Anthrapyridone dyestuffs



United States Patent 3,369,023 ANTHRAPYRIDONE DYESTUFFS Guido R. Genta,Dunustown, Lock Haven, Pa., assiguor to American Aniline Products, Inc.,a corporation of Delaware N0 Drawing. Filed Sept. 20, 1966, Ser. No.580,579 2 Claims. (Cl. 260278) This invention relates to anthrapyridonedyestuffs. In one specific aspect it relates to new anthrapyridonessubstituted with mercapto groups in the 4-position. The new dyes haveremarkable aflinity for polyester fibers and produce thereongreenish-yellow to golden-yellow shades.

Considerable effort has been expended in the dyestuffs industry in asearch for suitable materials to color aromatic polyester fibers, inparticular, polyethyleneterephthalate. Generally, the aromatic polyesterfibers have a poor affinity for dyestufis, since they do not readilyabsorb colorants from aqueous dispersions. As a result, it has beendiflicult to find dyes which are acceptable in all of the importantphysical properties of substantivity, light fastness, and resistance tosublimation. Many dyes which have passable aflinity for polyester fibersand which color these materials yellow to orange shades having areasonably satisfactory fastness to light, leave much to be desired withrespect to their fastness to sublimation. Others are inferior from thestandpoint of tinctorial strength or are limited in use by the methodwith which they can be effectively applied.

I have discovered a new class of anthrapyridone dyes which giveoutstanding over-all performance when dyed on aromatic polyester fibers,particularly on polyethyleneterephthalate. The afiinity for the fiber,light fastness, and resistance to sublimation of my new anthrapyridonecompounds is quite remarkable when considered in the light of theperformance of the anthraquinone dyes ordinarily used for this purpose.

Other valuable features of my new dyes are their outstanding tinctorialstrength and the ease with which they may be applied to polyesters byany of the conventional techniques, such as carrier dyeing orthermofixation. The increasing popularity of mixed fabrics, e.g.,polyester/ cotton, has made staining an important consideration forpolyester colors. My new dyes are excellent in this respect since theydo not stain cotton.

Thioaryloxyanthraquinones have been known for many years. It has beenrecently recognized in US. Patent 3,163,446 that certain dyes of thisclass are good colorants for hydrophobic textile materials, such aspolyethyleneterephthalate. Among the thioaryloxyanthraquinones disclosedin the patent are compounds having an acylamino group in the l-position,such as l-acetylamino-4- p-tolylmercaptoanthraquinone. Although suchcompounds give satisfactory results in most respects when applied tohydrophobic textile materials, my heretofore unknown dyes areunexpectedly superior, particularly in their tinctorial strength, theirresistance to sublimation, and in their dyeing of mixed fabrics.

It is therefore an object of the present invention to provide a newclass of greenish-yellow to golden-yellow colors for polyester fibers.

3,369,023 Patented Feb. 13, 1968 In accordance with the invention I havediscovered a new class of anthrapyridone dyes having the formula:

ii sz wherein R is a member selected from the group consisting of methyland ethyl and Z is a member selected from the group consisting of and CH(CH ),,OH, wherein R is a member selected from the group consisting ofhydrogen, chlorine, bromine, and lower alkyl; R is a member selectedfrom the group consisting of hydrogen and lower alkyl; X is a memberselected from the group consisting of hydrogen, chlorine, and bromine;and n is an integer having a value of 15.

The dyes of the invention are made by reacting a 4-halo-l:9(N)-alkylanthrapyridone with the appropriate mercaptan in thepresence of a suitable halogen acceptor, such as potassium carbonate.The product is recovered from the reaction mixture by standard methods.

The anthrapyridone intermediates useful in making the dyes of theinvention, e.g., 4-bromo-1:9(N)-methylanthrapyridone, and4-bromo-l:9(N)-ethylanthrapyridone, are commercially available. Ifdesired, these intermediates 4 can be easily made by acetylation of1-methylamino-4- bromoanthraquinone or l-ethylamino 4 bromoanthraquinonewith acetic anhydride in the presence of a trace of sulfuric acid as acatalyst. The resulting acetylalkylamino-4-bromoanthraquinone isring-closed to form the desired intermediate by boiling with dilutecaustic soda.

Mercaptans useful as intermediates for the dyes of the invention includethiophenol, o-, m-, and p-chlorothiophenol, 0-, mand p-bromothiophenol,p-methylthiophenol, p-t-butylthiophenol, mixed thioxylenols,benzylmercaptan, p-chlorobenzylmercaptan, p-bromobenzylmercaptan,mercaptoethanol, mercaptopropanol, and the like.

The dyes of the invention are made by reacting one mole of theanthrapyn'done intermediate with one mole of the desired mercaptan inthe presence of a polar organic solvent, preferably a solvent having aboiling point of at least 120 C. Useful solvents include ethylene,glycol monomethyl ether, ethylene glycol monoethyl ether, namyl alcohol,Cellosolve acetate, diacetone alcohol, ethylene glycol, benzyl alcohol,diethylene glycol, butyl Cellosolve, sulfolane, dimethylformamide,dimethylacetamide, and the like. Lower boiling polar organic solvents,such as ethanol, can also be used for the reaction, but the use of suchsolvents places practical limits upon the reaction temperature that canbe used.

3 The reaction takes place at a temperature between about 60 C. and theboiling point of the particular solvent used. At temperatures belowabout 60 C., the reaction does not proceed at a commercially usefulrate.

ance to sublimation and excellent light fastness by both the standardcarrier dyeing and thermo-fixation methods. A notable feature of the newdye was its reserve (nonstaining) of cotton when applied to mixedpolyester/ The preferred reaction temperature is between 100 and 5cotton fabrics. 140 C. If desired, the reaction can be carried out underE l H an inert atmosphere, e.g., nitrogen gas, to protect the thioxamp ephenol from oxidation To the 560 ml. flask equipped as described inExample The reaction is carried out in the presence of a halogen I thereWfire charged 250 fiihylehe g y mohoe'thyl acceptor, preferably analkali metal hydroxide, an alkali 1O ether, 9 4-t-bl1tY1thi0Pheh01, and7 POtaSSium metal carbonate, or an alkali metal acetate. Useful halon Tr i g mixture was a d to 7 and gen acceptors include potassiumhydroxide, sodium hy- 17 gof 4-bY0Ih0-1I9(N)'mefhylamhrapyridone Wasdroxide, sodium carbonate, potassium carbonate, sodium added Slowlythereto- The miXhlre W218 heatfid for a acetate, and the like. At leastone equivalent of halogen Period of 12 hours at 110-115 mi iherfiaftel'COOIfid acceptor is required for each halogen present on the 15 to roomtemperature with agitation, the mixture Was anthrapyridone intermediate,A excgg f halogen diluted with 100 ml. of ethanol. *It was thereafterfiltered ceptor can be used, but no particular advantage is 0band washedwith alcohol, water, and 50 percent alcohol. tained thereby. Upon dryingthere was obtained 21.2 g. of substantially The reaction generally takesfrom 10-30 hours. After p re P The dyeshlfi Was add pasted and Standthereaction is complete, the mixture is allowed tocool a i d as describedin Example I as a 10 percent paste. to ambient temperature. The productis separated by It y Dacron polyester fiber in a reddish t0goldenfiltration and, if desired, washed with alcohol, water, or yellowshade having y g li a i n pr p r i both, and excellent light fastness.

The dyestuli is applied to textile fibers in the form of a dispersedcolor powder or paste, which is obtained Example y Wet milhhg y aconventional apparatus, h To the 500 ml. flask equipped as described inExample as a ball mill, w th a dispersant, such as sodium lignrn 1 therewere charged m1. of ethanol, 7 bgnzylmer. sulflhate; a Wetting agent;and a Sultable q y of captan, and 7 g. potassium carbonate. The mixturewas water. Sufficient diluent or standardizing agent is added heated toQ and there were added 17 g. f to adjust the dyestulf to a standardstrength. The dispersed 4 ;9(N) methylanthrapyridone The mixture wascake Paste can also he p y dried Oven dried and heated to reflux at 7882C. and held at this temperathereafter micropulverized if desired.Sufiicient dispersant ture f 1 hours o h d d of ethylene glycol andStandardizing agents are added to give a dispersed monoethyl ether wasadded with stirring and the mass Powder gehel'ally Containing hem/66Habout 10-60 Percent was cooled to room temperature. It was then filteredand active (Pure) dyesfufi base; The dismal-36d Powder, when washed withalcohol and water until it was alkali free. added to l Wlth 'E Y forms A16 g. quantity of the desired product was obtained. a near colloidalaqueous dispersion in which the goods Th dye tutf was standardized asdescribed in Example I are 1n h cfnventlonal manneras a 14 percentpaste. It dyed Dacron polyester fiber My invention is furtherillustrated by the following in a reddish to goldemyehow Shade havingExcellent examples: 4o sublimation properties and excellent lightfastness.

Example 1 Example IV T 0 a 500 ml. flask equipped with heater, stirrer,ther- To the 500 flask equipped as described in Example mometer, andreflux condenser there were charged 700 I there were charged 300ethylene glycol monoethyl ethylene glycol mohoellhyl ether, 24thlophehol, ether, 10 g. mercaptoethanol, and 14 g. potassium car- 28 g.potassium carbonate. The reaction mass was heated honate The mixture washeated to C. and there to 75 C. with stirring and 68 g.4-bromo-l:9(N)rnethylwas slowly added 34 4 1;9 anthraPYTidPne was addedat a slow rateh P P pyridone. The temperature was raised to l10ll5 C.ture was raised to 1 was malhtalned and held overnight. After cooling toroom temperature, Period of 16 After coohng to Cw the the mass wasfiltered, washed with 50 percent alcohol mass was filtered and theYellow needle-like crystals and water until alkali free, and thereafterdried. There thus obtained were washed alkali free with cold water. Wasthus obtained 5 f yellow crystals The d ff A 60 q y of substahtially P f4-thiophehoxy was standardized as described in Example I. It dyed )h y hpy Was Obtained The Product Dacron polyester fiber in a yellow shadehaving excellent had a resldual bromme content of Percent sublimationproperties and excellent light fastness.

The g. of pure dye was ball milled for 24 hours with 15 g. sodium ligninsulfonate dispersant available Examples V X commercially as MarasperseN, 15 g. wetting agent, and ml. of water. 60 By following the proceduredescribed in Example I The 22 percent paste thus obtained dyed Dacronpolywith the mercaptan shown below in Table -I, the foltester fiber ingreenish-yellow shades with excellent resistlowing results are obtained:

TABLE I Fastness on Polyester Example No. Reactant Product LightSublimation V p-Chlorothiophenol4-(p-chlorothiophenoxy)-1:(N)-methylauthrapyridone Excellent...Excellent. VI p-Bromothiophenol4-(p-bromothiophenuxy)-1:9(N)-ethylanthrapyridoue .do Do. VIIp-MethylthiophenoL. 4-(p-methylthiophenoxy)-1:9(N)-methylanthrapyridone.do Do. VIII Mixed thioxylenols4-(thioxyloxy)-l.9(N)-methylanthrapyridine undo. Very good. IX.Mercaptopropanol 4-(thiohydropropoxy)-l:2(N)-rnethylanthrapyridone ..do.Excellent.

- p-Ohlorobenzylmercapta4-(pchlorobenzylmercapto)-1:9(N)metllylanthrapyriodone "do Do.

5 I claim: 1. A dye of the formula:

1 A; HO N-GH;

| 0 SQMHH:

6 2. A dye of the formula:

Hjl i| I-CH3 0 S-OZHEOH References Cited UNITED STATES PATENTS 6/1953Randall et a1. 260--278 3/1964 Blout et a1. 260-278 1/1965 Altermatt260-369 ALEX MAZEL, Primary Examiner.

D. G. DAUS, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,369,023 February 13 1968 Guido R. Genta It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 5, lines 1 to 10, the formula should appear as shown belowinstead of as in the patent:

C HC N-CH column 6, lines 1 to 10, the formula should appear as shownbelow instead of as in the patent:

HC NCH Signed and sealed this 13th day of May 1969.

(SEAL) Attest:

1. A DYE OF THE FORMULA: